CN115354150B - Biomass carbon-containing pellet for blast furnace ironmaking and preparation method thereof - Google Patents
Biomass carbon-containing pellet for blast furnace ironmaking and preparation method thereof Download PDFInfo
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- CN115354150B CN115354150B CN202210905569.7A CN202210905569A CN115354150B CN 115354150 B CN115354150 B CN 115354150B CN 202210905569 A CN202210905569 A CN 202210905569A CN 115354150 B CN115354150 B CN 115354150B
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- 239000002028 Biomass Substances 0.000 title claims abstract description 235
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 178
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 239000008188 pellet Substances 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000003763 carbonization Methods 0.000 claims abstract description 53
- 239000011230 binding agent Substances 0.000 claims abstract description 41
- 238000000605 extraction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000012943 hotmelt Substances 0.000 claims abstract description 32
- 239000003610 charcoal Substances 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000000197 pyrolysis Methods 0.000 claims abstract description 27
- 238000003723 Smelting Methods 0.000 claims abstract description 25
- 238000000465 moulding Methods 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims description 70
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- 230000004907 flux Effects 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 10
- 229910052595 hematite Inorganic materials 0.000 claims description 9
- 239000011019 hematite Substances 0.000 claims description 9
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002154 agricultural waste Substances 0.000 claims description 3
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 229910052839 forsterite Inorganic materials 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010815 organic waste Substances 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000002803 fossil fuel Substances 0.000 description 5
- 238000007731 hot pressing Methods 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 239000002296 pyrolytic carbon Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002529 flux (metallurgy) Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical group [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
- C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides biomass carbon-containing pellets for blast furnace ironmaking and a preparation method thereof, wherein biomass hydrothermal carbon with low alkali metal content and high hot melt extraction rate is prepared by crushing biomass and then carrying out hydrothermal carbonization; performing pyrolysis carbonization treatment on one part of the biomass hydrothermal carbon to prepare low-volatile biomass carbon, and performing hot-melt extraction on the other part of the biomass hydrothermal carbon to prepare a biomass high-temperature binder; and crushing and uniformly mixing biomass charcoal, a biomass high-temperature binder, iron ore powder and a solvent, and performing hot press molding to obtain biomass carbon-containing pellets. Through the mode, the biomass with high volatile, high moisture and high harmful element content can be prepared into the biomass-based reducing agent with high fixed carbon content, high cohesiveness and low harmful element content and the binder, and the high-quality biomass carbon-containing pellets which can be used as blast furnace smelting furnace burden are prepared through a hot press forming method, so that the carbon emission in the iron-making production process is effectively reduced.
Description
Technical Field
The invention relates to the technical field of blast furnace low-carbon ironmaking, in particular to biomass carbon-containing pellets for blast furnace ironmaking and a preparation method thereof.
Background
Compared with the traditional fossil fuel, biomass energy is taken as a product of photosynthesis of plants, has the characteristics of high yield, reproducibility and neutrality of carbon, is the only renewable carbon-containing clean energy source, and has great application potential in the field of industrial production. If the abundant biomass resources can be applied to iron-making production, on one hand, the dependence of the traditional blast furnace iron-making process on fossil energy sources can be reduced, and fossil fuel CO in the steel production process can be reduced 2 Discharging; on the other hand, a large amount of agricultural and forestry wastes can be consumed, the influence of open-air combustion on the environment is reduced, and the utilization efficiency of the wastes is improved. At present, agriculture and forestry waste lifeThe application research of material resources in iron-making production mainly focuses on procedures such as blast furnace blowing, coking, sintering, preparation of oxidized pellets and carbon-containing pellets. Research results show that the biomass has potential of being applied to iron-making production, and opens up a new path for the development of low-carbon iron-making technology.
The carbon-containing pellets are spherical furnace charges formed by fully mixing and pressing iron ore powder, coking coal or coal dust and other carbon-containing materials, the main purpose of the carbon-containing pellets studied initially abroad is to be used for non-blast furnace ironmaking, and in recent years, the carbon-containing pellets are gradually considered to be used in a blast furnace as novel furnace charges along with the deep research. The main advantages of the novel burden containing carbon pellets, which replaces the traditional burden (sinter, pellet and lump ore) applied to blast furnace smelting, are that the reduction equilibrium temperature in the blast furnace can be reduced, the smelting with low coke ratio and low fuel ratio is realized, and the improvement of the blast furnace efficiency and the reduction of CO are facilitated 2 And (5) discharging. The biomass is utilized to replace traditional fossil energy to prepare the carbon-containing pellets, and on the basis of realizing the energy conservation and emission reduction effects of the traditional carbon-containing pellets, the property of carbon neutrality of the biomass is combined with the iron-making production of CO 2 The implementation of the removal, utilization and sequestration (CCUS) technology will further drive the early realization of low carbon, zero carbon, and even carbon negative production in steel manufacturing.
The carbon-containing pellets are divided into cold-pressed carbon-containing pellets and hot-pressed carbon-containing pellets according to the molding temperature. The cold-pressed carbon-containing pellets are formed at normal temperature or low temperature, but a large amount of adhesive is needed, so that the problems of high-temperature strength failure, slag quantity increase and the like are easily caused. The hot-pressed carbon-containing pellet is a carbon-iron composite furnace charge which is formed by heating thermoplastic coal powder and iron-containing powder to a certain temperature and pressing in a hot state. The temperature of the hot-pressed carbon-containing pellet material is higher than that of the cold-pressed carbon-containing pellet, and the hot-pressed carbon-containing pellet provides good reduction dynamics conditions due to the close contact of coal and ore, so the hot-pressed carbon-containing pellet material has excellent reduction performance and better high-temperature strength. Therefore, an attempt is necessary to prepare biomass carbon-containing pellets by adopting a hot press molding technology, so that the efficient utilization of biomass resources in iron-making production is realized.
The patent with publication No. CN104975173A provides a method for producing fluxed composite carbon-containing pellets for blast furnaces, which comprises the steps of mixing a certain amount of iron ore concentrate, an adhesive, a carbon-containing material and a flux into a mixture A, adding water into the mixture A, and uniformly mixing the mixture A to prepare self-fluxing pellet cores; then mixing iron ore concentrates, adhesives, carbonaceous materials and fluxes with different dosages to form a mixture B, blending self-fluxing pellet cores with the mixture B to form pellets, preparing raw pellets of the carbonaceous pellets, and roasting to obtain the fluxed composite carbonaceous pellets. The patent uses biomass charcoal as a carbon-containing material in the mixture A, and can realize the utilization of biomass resources in iron-making production to a certain extent, but the performance of the biomass charcoal and the preparation method thereof are not controlled, and the performance of the biomass charcoal has important influence on the performance of the finally prepared carbon-containing pellets and the practical application effect thereof.
In fact, most of the existing biomass charcoal has the problems of higher alkali metal content and higher volatile matter content, and the existence of alkali metal can have negative influence on the performance of the carbon-containing pellets and the blast furnace smelting, and a large amount of volatile matters are separated out in the heating process of the carbon-containing pellets to easily cause abnormal expansion of the pellets to cause cracking of the pellets. In addition, the preparation of biomass carbon-containing pellets by adopting a hot press forming technology ensures that the biomass carbon-containing pellets can be effectively formed under hot press and improves the high-temperature performance of the biomass carbon-containing pellets so as to meet the requirements of blast furnace smelting production, which is a current urgent problem to be solved.
In view of the above, there is a need to design an improved biomass carbon-containing pellet for blast furnace ironmaking and a preparation method thereof to solve the above problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide biomass carbon-containing pellets for blast furnace ironmaking and a preparation method thereof, which are characterized in that biomass with high volatile, high moisture and high harmful element content is prepared into biomass-based reducing agents and binders with high fixed carbon content, high cohesiveness and low harmful element content by adopting hydrothermal carbonization, pyrolysis carbonization and hot-melt extraction methods, and the biomass-based reducing agents and binders with high fixed carbon content and low harmful element content are prepared into high-quality biomass carbon-containing pellets by adopting a hot-press molding method, so that the biomass carbon-containing pellets can be used as blast furnace smelting burden.
In order to achieve the above purpose, the invention provides a preparation method of biomass carbon-containing pellets for blast furnace ironmaking, which comprises the following steps:
s1, removing impurities from biomass raw materials, crushing, and preparing biomass hydrothermal carbon with alkali metal content lower than 0.3% and hot-melt extraction rate higher than 15% by adopting a hydrothermal carbonization technology;
s2, carrying out pyrolysis carbonization treatment on part of the biomass hydrothermal carbon prepared in the step S1 to prepare biomass carbon with the volatile content lower than 15%; carrying out solvent hot-melting extraction on the other part of the biomass hydrothermal carbon to prepare a biomass high-temperature binder;
s3, respectively crushing the iron ore powder, the flux and the biomass charcoal and the biomass high-temperature binder prepared in the step S2, and uniformly mixing to obtain a mixture;
and S4, performing hot press molding on the mixture obtained in the step S3 to obtain biomass carbon-containing pellets.
As a further improvement of the invention, in the step S1, the hydrothermal carbonization temperature of the hydrothermal carbonization technology is 200-260 ℃, the hydrothermal carbonization time is 60-180 min, and the solid-liquid ratio of the biomass raw material and water is 1:3-1:5; the ash content of the prepared biomass hydrothermal carbon is lower than 7.5%, the volatile matter is lower than 65.8%, and the sulfur content is lower than 0.2%.
As a further improvement of the invention, in the step S2, the pyrolysis carbonization temperature is 500-900 ℃, and the pyrolysis carbonization time is 60-240 min; the ash content of the prepared biomass charcoal is lower than 10.6%.
As a further improvement of the invention, in the step S2, the temperature of the hot-melt extraction is 280-420 ℃, the solid-liquid ratio of the biomass hydrothermal carbon to the solvent in the hot-melt extraction process is 1:5-1:80, the time of the hot-melt extraction is 30-120 min, and the solvent is an organic solvent; preferably, the solvent is N-methylpyrrolidone; the ash content of the prepared biomass high-temperature binder is less than 3.5%, the volatile content is less than 55.6%, and the caking index is more than 81.3%.
As a further improvement of the invention, in the step S3, after the crushing, the mass fractions of the particles with the granularity smaller than 0.074mm in the biomass charcoal, the biomass high-temperature binder, the iron ore powder and the flux are respectively larger than 60%, 30%, 70% and 80%; the mass ratio of the biomass charcoal to the biomass high-temperature binder to the iron ore powder to the flux in the mixture is 20-30:5-10:70-75:3-5; preferably, the mass ratio is 25:8:73:4.
As a further improvement of the invention, in the step S4, the temperature of the hot press molding process is 350-550 ℃, the pressure is more than 15MPa, and the hot press time is more than 1min.
As a further improvement of the present invention, in the step S3, the iron ore powder is one or more of hematite, magnetite, limonite, vanadium titanomagnetite, sea sand ore and baiyuneboite, and the flux is one or more of quicklime, slaked lime, dolomite, serpentine and forsterite.
As a further improvement of the invention, the biomass raw material is one or a mixture of more of agricultural waste, forestry waste and urban organic waste.
In order to achieve the above purpose, the invention provides biomass carbon-containing pellets for blast furnace ironmaking, which are prepared by adopting the preparation method according to any one of the technical schemes, and can replace sinter or pellet ore to be applied to blast furnace smelting.
As a further improvement of the invention, the cold state strength of the biomass carbon-containing pellets is more than 1000N/piece, the high-temperature reduction strength is more than 500N/piece, the reducibility is more than 75%, the reduction expansion index is less than 10%, and the low-temperature reduction degradation index is more than 92%.
The beneficial effects of the invention are as follows:
(1) The preparation method of biomass carbon-containing pellets for blast furnace ironmaking provided by the invention prepares biomass with high volatile, high moisture and high harmful element content into biomass-based reducing agent and binder with high fixed carbon content, high cohesiveness and low harmful element content by adopting hydrothermal carbonization, pyrolysis carbonization and hot-melt extraction methods, and prepares the high-quality biomass carbon-containing pellets by adopting a hot-press molding method. Here, theOn the basis, the biomass carbon-containing pellets prepared by the method can be used as blast furnace smelting furnace burden, so that the consumption of coke in iron-making production can be reduced, and the discharge of carbon dioxide and pollutants in the iron-making production process can be reduced. In addition, the biomass carbon-containing pellets formed by hot pressing have the characteristics of high cold strength and hot strength, good reducibility and excellent soft melting dripping characteristic, can be applied to blast furnace smelting production in a large proportion, and can realize the energy consumption of the blast furnace smelting and the reduction of CO 2 The emission is of great significance.
(2) According to the invention, through the synergistic use of the hydrothermal carbonization and pyrolysis carbonization processes and further the regulation and control of the parameters of the hydrothermal carbonization and pyrolysis carbonization processes, the prepared high-quality biomass charcoal has the characteristics of low alkali metal content, low ash content, low volatile matter content and high fixed carbon content, so that the extremely low content of alkali metal harmful elements in the prepared biomass carbon-containing pellets is ensured, the alkali load is not greatly increased when the biomass carbon-containing pellets are applied to the blast furnace production in batches, the negative influence of alkali metal on the carbon-containing pellets and the blast furnace smelting is effectively avoided, and the negative influence of alkali metal and volatile matter precipitation on the pellet strength in the heating reduction process of the carbon-containing pellets is avoided.
(3) According to the invention, the biomass hydrothermal carbon with high hot-melt extraction rate is prepared, and then the biomass hydrothermal carbon is prepared into the biomass-based high-temperature binder in a hot-melt extraction mode, so that the utilization rate of biomass raw materials is improved, the problem that the biomass carbon is difficult to hot-press molding due to no thermoplasticity is effectively solved, the use of an inorganic binder is avoided, the introduction of impurities is avoided, and the grade of biomass carbon-containing pellets is improved. Meanwhile, the biomass high-temperature binder prepared by the method can be used for bonding and molding materials such as iron ore powder and a reducing agent through hot pressing at normal temperature so as to achieve higher cold strength, and can be used for coking and carbonizing in a high-temperature heating process so as to form stronger high-temperature strength, so that the requirements of blast furnace smelting production are met.
(4) The invention prepares the high-quality carbon-containing pellets which can be used for blast furnace smelting by taking biomass as a raw material, effectively improves the comprehensive utilization efficiency of biomass resources, and reduces the pairing of blast furnace ironmaking productionConsumption of fossil fuel and reduction of CO produced by iron and steel 2 The discharge amount has obvious economic, social and ecological benefits.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of biomass carbon-containing pellets for blast furnace ironmaking.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of biomass carbon-containing pellets for blast furnace ironmaking, which has a flow diagram shown in figure 1 and comprises the following steps:
s1, removing impurities from biomass raw materials, crushing, and preparing biomass hydrothermal carbon with alkali metal content lower than 0.3% and hot-melt extraction rate higher than 15% by adopting a hydrothermal carbonization technology;
s2, carrying out pyrolysis carbonization treatment on part of the biomass hydrothermal carbon prepared in the step S1 to prepare biomass carbon with the volatile content lower than 15%; carrying out solvent hot-melting extraction on the other part of the biomass hydrothermal carbon to prepare a biomass high-temperature binder;
s3, respectively crushing the iron ore powder, the flux and the biomass charcoal and the biomass high-temperature binder prepared in the step S2, and uniformly mixing to obtain a mixture;
and S4, performing hot press molding on the mixture obtained in the step S4 to obtain biomass carbon-containing pellets.
According to the technical scheme, the biomass raw material is mixed with water according to a certain proportion after being subjected to impurity removal and crushing, the mixture is placed into a reaction kettle for hydrothermal carbonization treatment, and the moisture, volatile matters and ash in the biomass are partially removed to prepare biomass hydrothermal carbon; then dividing the biomass hydrothermal charcoal into two parts, wherein one part is subjected to pyrolysis carbonization treatment, so that volatile matters in the biomass hydrothermal charcoal are further removed, and the volatile matters are reduced to be less than 15%, so that high-quality biomass pyrolysis charcoal is obtained; and extracting viscous components in the biomass hydrothermal carbon by adopting a hot-melt extraction technology to prepare the biomass high-temperature binder. And respectively crushing the prepared biomass pyrolytic carbon, the biomass high-temperature binder, the iron ore powder and the flux, uniformly mixing, and treating the uniformly mixed raw materials by adopting a pressure forming technology to obtain biomass carbon-containing pellets. The biomass carbon-containing pellets prepared by the method can be used as blast furnace smelting furnace burden, can reduce the consumption of coke in iron-making production, and reduce CO in the iron-making production process 2 And the amount of pollutant emissions.
Further, in the step S1, the hydrothermal carbonization temperature of the hydrothermal carbonization technology is 200-260 ℃, the hydrothermal carbonization time is 60-180 min, and the solid-liquid ratio of the biomass raw material to water is 1:3-1:5; the ash content of the prepared biomass hydrothermal carbon is lower than 7.5%, the volatile matter is lower than 65.8%, and the sulfur content is lower than 0.2%; the biomass raw material is one or a mixture of more of agricultural waste, forestry waste and urban organic waste.
In the step S2, the pyrolysis and carbonization temperature is 500-900 ℃, and the pyrolysis and carbonization time is 60-240 min; the ash content of the prepared biomass charcoal is lower than 10.6%; the temperature of the hot-melt extraction is 280-420 ℃, the solid-to-liquid ratio of the biomass hydrothermal carbon to the solvent in the hot-melt extraction process is 1:5-1:80, the time of the hot-melt extraction is 30-120 min, and the solvent is an organic solvent; preferably, the solvent is N-methylpyrrolidone; the ash content of the prepared biomass high-temperature binder is less than 3.5%, the volatile content is less than 55.6%, and the caking index is more than 81.3%.
In the step S3, after the crushing, the mass fractions of particles with the granularity smaller than 0.074mm in the biomass charcoal, the biomass high-temperature binder, the iron ore powder and the flux are respectively larger than 60%, 30%, 70% and 80%; the mass ratio of the biomass charcoal to the biomass high-temperature binder to the iron ore powder to the flux in the mixture is 20-30:5-10:70-75:3-5; preferably, the mass ratio is 25:8:73:4; the iron ore powder is one or more of hematite, magnetite, limonite, vanadium titano-magnetite, sea sand ore and baiyuneboite, and the flux is one or more of quicklime, slaked lime, dolomite, serpentine and forsterite.
In the step S4, the temperature of the hot press forming process is 350-550 ℃, the pressure is more than 15MPa, and the hot press time is more than 1min.
The invention also provides biomass carbon-containing pellets for blast furnace ironmaking, which are prepared by adopting the preparation method in the technical scheme, and can replace sinter or pellet ore to be applied to blast furnace smelting.
The cold state strength of the biomass carbon-containing pellets is more than 1000N/biomass carbon-containing pellets, the high-temperature reduction strength is more than 500N/biomass carbon-containing pellets, the reducibility is more than 75%, the reduction expansion index is less than 10%, and the low-temperature reduction degradation index is more than 92%.
The biomass carbon-containing pellets for blast furnace ironmaking and the preparation method thereof provided by the invention are specifically described below with reference to specific examples.
Example 1
The embodiment provides a preparation method of biomass carbon-containing pellets for blast furnace ironmaking, which takes corn stalks from a farm as biomass raw materials and specifically comprises the following steps:
s1, preparing biomass hydrothermal carbon
Removing impurities such as iron wires and soil from the collected corn stalks by using an iron remover and a vibrating screen, crushing the corn stalks into particles with the granularity smaller than 8mm by using a crusher, filling the crushed soybean stalks and water into a high-pressure reaction kettle according to a solid-to-liquid ratio of 1:3, heating the reaction kettle after sealing, controlling the reaction temperature to 260 ℃, and preserving heat for 60 minutes after reaching the reaction temperature. And after the hydrothermal carbonization reaction is finished, cooling and depressurization is carried out on the reaction product, the reaction product is transferred to a solid-liquid separation device to separate a solid product from a liquid product, so that the hydrothermal carbon is obtained, the liquid product is partially recycled after deoiling, and part of the liquid product is discharged to ensure that alkali metal elements in the biomass hydrothermal carbon are not out of standard. The hydrothermal carbon is subjected to component detection after being dried, the volatile content of a drying base is 40.2%, the ash content of the drying base is 2.3%, the alkali metal content of the drying base is 0.12%, and the sulfur content of the drying base is 0.03%.
S2, preparing biomass charcoal and biomass high-temperature binder
Dividing the dried biomass hydrothermal charcoal into two parts, wherein one part is subjected to pyrolysis carbonization, the pyrolysis carbonization temperature is 600 ℃, the pyrolysis carbonization time is 200min, the ash content of the biomass pyrolysis charcoal obtained by pyrolysis is 3.7%, and the volatile content is 13.8%. The other part of biomass hydrothermal carbon is subjected to hot-melt extraction, the organic solvent is N-methyl pyrrolidone, the hot-melt extraction temperature is 340 ℃, the solid-liquid ratio is 1:6, the extraction time is 70min, the extracted reactant is filtered, the liquid phase is used for fractionating the organic solvent in a distillation container, the residue is a biomass high-temperature binder, the hot-melt extraction rate of the prepared biomass high-temperature binder is 25.7%, the ash content is 0.7%, the volatile component is 46.8%, and the cohesiveness index is 95.6%.
S3, preparing a mixture
The method comprises the steps of selecting hematite fine powder provided by a certain domestic iron and steel enterprise as a raw material, using limestone as a flux, crushing biomass charcoal, a biomass high-temperature binder, hematite fine powder and limestone by using a crusher, wherein the proportion of parts of the crushed biomass charcoal, the crushed biomass high-temperature binder, the crushed hematite fine powder and the crushed limestone, with the granularity smaller than 0.074mm, is respectively larger than 65%,35%,90% and 85%. And heating the biomass charcoal to 250 ℃ by using a heating device, heating the biomass high-temperature binder to 130 ℃, heating the hematite fine powder and the limestone to 500 ℃, and mixing the biomass charcoal, the biomass high-temperature binder, the hematite fine powder and the solvent according to the mass ratio of 25%, 8%, 73% and 4%, wherein the temperature of the mixed material is 410 ℃.
S4, preparing biomass carbon-containing pellets by hot press molding
And loading the mixed materials into a twin-roll pelletizing device for preparing biomass carbon-containing pellets, wherein the hot pressing pressure is 40MPa, the hot pressing time is 3min, and naturally cooling the materials after the hot pressing technology to obtain the biomass carbon-containing pellets.
And detecting metallurgical performance of the cooled biomass carbon-containing pellets, wherein the cold state strength is 1250N/each, the reduction strength is 556N/each at 900 ℃, the reduction strength is 780N/each at 1000 ℃, the reduction strength is 1538N/each at 1100 ℃, the reduction strength is 2155N/each at 1200 ℃, the reducibility is 88%, the reduction expansion index is 5%, and the low-temperature reduction degradation index is 94%.
Based on the steps, the biomass carbon-containing pellets obtained in the embodiment have extremely low content of alkali metal harmful elements, and the alkali load is not greatly increased when the biomass carbon-containing pellets are applied to the blast furnace production in batches, so that the negative influence of alkali metal on the carbon-containing pellets and the blast furnace smelting is avoided. Meanwhile, the biomass carbon-containing pellets prepared by the embodiment have higher cold state strength and hot strength, the reducibility, the reduction expansibility and the low-temperature reduction degradation performance are better than those of the traditional sinter, pellet and lump ore, the biomass carbon-containing pellets can be directly used as blast furnace burden, the consumption of blast furnace smelting on coke is effectively reduced, further the iron-making cost and carbon emission are reduced, and the biomass carbon-containing pellets have remarkable economic, social and ecological benefits.
Examples 2 to 5
Examples 2 to 5 respectively provide a preparation method of biomass carbon-containing pellets for blast furnace ironmaking, compared with example 1, the difference is that the hydrothermal carbonization conditions are changed, the hydrothermal carbonization temperature, the hydrothermal carbonization time and the technical indexes of the obtained hydrothermal carbon are shown in table 1, and other preparation methods and the same as in example 1 are not repeated here.
Table 1 conditions for preparation of examples 2 to 5 and technical indices of the prepared hydrothermal carbons
The performance of the biomass carbon-containing pellets prepared in examples 2 to 5 was tested and the results are shown in table 2.
Table 2 properties of biomass carbon-containing pellets prepared in examples 2 to 5
| Examples | Example 2 | Example 3 | Example 4 | Example 5 |
| Intensity of cold state (N/P) | 1230 | 1320 | 1050 | 880 |
| Reduction Strength at 900 ℃ (N/P) | 530 | 655 | 515 | 502 |
| Reduction Strength at 1000 ℃ (N/N) | 828 | 915 | 801 | 760 |
| Reduction Strength at 1100 ℃ (N/P) | 1673 | 1766 | 1587 | 1456 |
| Reduction strength (N/N) at 1200 DEG C | 2322 | 2539 | 2232 | 2016 |
| Reducibility (%) | 89 | 87 | 93 | 94 |
| Reduction expansion index (%) | 5.6 | 4.8 | 6.3 | 7.1 |
| Low temperature reduction degradation index (%) | 93 | 95 | 93 | 92 |
As can be seen from Table 1, the dry base volatile components of the hydrothermal carbons prepared in examples 2 to 5 are between 39.1% and 46.7%, the ash content is 2.1% to 2.6%, the alkali metals are all lower than 0.15, the sulfur content is very low and is all lower than 0.03%, the sulfur content is very low and is the level of extremely low sulfur coal, and the hot-melt extraction rates are all higher than 15%, so that the hot-melt extraction rates are obviously improved compared with the hot-melt extraction rates of only 1% to 3% when biomass is directly used for hot-melt extraction. The influence of the hydrothermal carbonization temperature and carbonization time on the prepared hydrothermal carbon components can be found that the influence of changing the biomass hydrothermal carbonization temperature is more obvious, and the volatile matters and ash contents of the hydrothermal carbon drying base are gradually reduced along with the increase of the hydrothermal carbonization temperature. The main reason is that the higher hydrothermal carbonization temperature can promote the degradation of main components such as cellulose, hemicellulose, lignin and the like in the biomass raw material, quicken the removal of volatile matters, and meanwhile, the water-soluble mineral matters contained in the biomass raw material are removed along with the degradation reaction, so that the ash content, alkali metal content and sulfur content in the preparation of the hydrothermal carbon are reduced.
As can be seen from table 2, the biomass hydrothermal carbon obtained by the preparation is used as a raw material to further prepare high-quality biomass pyrolytic carbon and a biomass high-temperature binder, and the biomass carbon-containing pellets prepared by the hot press molding method have cold state strength of 880N/m-1320N/m, reduction strength of 900 ℃ of 502N/m-655N/m, reduction strength of 1000 ℃ of 760N/m-915N/m, reduction strength of 1100 ℃ of 1456N/m-1766N/m, reduction strength of 1200 ℃ of 2016N/m-2539N/m, reduction performance of 87% -94%, reduction expansion index of 4.8% -7.1% and low-temperature reduction pulverization index of 92% -95%. Although the metallurgical properties of biomass carbon-containing pellets prepared under different conditions are different to a certain extent, the requirements of blast furnace smelting can be met, the biomass carbon-containing pellets can be directly used as blast furnace burden, the consumption of fossil fuel by blast furnace smelting is reduced, and the method has remarkable economic, social and ecological benefits.
Examples 6 to 10
Examples 6 to 10 respectively provide a method for preparing biomass carbon-containing pellets for blast furnace ironmaking, which is different from example 4 in that the parameters of the pyrolysis carbonization process are changed. The pyrolysis carbonization temperature, pyrolysis carbonization time, hot-melt extraction temperature, hot-melt extraction time and corresponding hot-melt extraction rate of examples 6 to 10 are shown in table 3, and other preparation methods and the same as example 4 are not described here again.
TABLE 3 preparation parameters for examples 6-10
The performance of the biomass carbon-containing pellets prepared in examples 6 to 10 was tested and the results are shown in table 4.
Table 4 properties of biomass carbon-containing pellets prepared in examples 6 to 10
As can be seen from Table 4, the biomass carbon-containing pellets obtained in examples 6 to 10 were produced to have a cold strength of 1410N/per unit of-1567N/per unit of 611N/per unit of-677N/per unit of reduction strength at 900 ℃, a reduction strength of 876N/per unit of-935N/per unit of 1000 ℃, a reduction strength of 1676N/per unit of-1788N/per unit of 1100 ℃, a reduction strength of 2517N/per unit of-2531N/per unit of 1200 ℃, a reduction property of 84 to 86%, a reduction expansion index of 4.2 to 4.7% and a low-temperature reduction pulverization index of 92 to 95%. The cold strength between samples prepared in different examples is greatly different, mainly because the high-temperature binder has improved cohesiveness along with the rise of the hot-melt extraction temperature, and the hot-pressed pellets have higher compressive strength. The strength after reduction is obviously different along with the rise of the pyrolysis carbonization temperature, and under the condition of low reduction temperature, the reduction strength of biomass carbon-containing pellets has positive correlation with the performance of a high-temperature binder, and the strength at the moment is correlated with the carbon network structure formed by the consolidation carbonization of the binder. The reduction strength of biomass carbon-containing pellets under the high-temperature reduction condition is more relevant to the performance of pyrolytic carbon, the higher the pyrolysis carbonization temperature is, the more compact the prepared biomass pyrolytic carbon microcrystalline structure is, the higher the temperature is needed to reduce iron oxide, the high-temperature strength is relevant to the newly-generated metal iron net structure, and the higher the generated metal iron amount is, the higher the strength is after high-temperature reduction. From table 4, it can be seen that the metallurgical properties of the biomass carbon-containing pellets prepared under different conditions are different to a certain extent, but the requirements of blast furnace smelting can be met, the biomass carbon-containing pellets can be directly used as blast furnace burden, the consumption of fossil fuel by blast furnace smelting is reduced, and the biomass carbon-containing pellets have remarkable economic, social and ecological benefits.
Examples 11 to 14
Examples 11 to 14 respectively provide a method for preparing biomass carbon-containing pellets for blast furnace ironmaking, which is different from example 4 in the types of iron ore powder, flux, molding temperature and molding pressure used, and specific values corresponding to the examples are shown in table 5. Other preparation methods and the same as example 4 are not described here.
TABLE 5 iron ore powder, solvent, forming temperature and forming pressure according to examples 11 to 14
The performance of the biomass carbonaceous pellets prepared in examples 11 to 14 was tested and the results are shown in table 6.
Table 6 properties of biomass carbon-containing pellets prepared in examples 11 to 14
| Examples | Example 11 | Example 12 | Example 13 | Example 14 |
| Intensity of cold state (N/P) | 1150 | 1028 | 1300 | 976 |
| Reduction Strength at 900 ℃ (N/P) | 645 | 610 | 733 | 538 |
| Reduction Strength at 1000 ℃ (N/N) | 878 | 819 | 703 | 788 |
| Reduction Strength at 1100 ℃ (N/P) | 1644 | 1528 | 1376 | 1489 |
| Reduction strength (N/N) at 1200 DEG C | 2555 | 2184 | 1784 | 1987 |
| Reducibility (%) | 86 | 83 | 76 | 81 |
| Reduction expansion index (%) | 4.5 | 4.2 | 4.2 | 4.0 |
| Low temperature reduction degradation index (%) | 95 | 93 | 90 | 93 |
As can be seen from table 6, the iron ore powder has a remarkable influence on the metallurgical performance of the prepared biomass carbon-containing pellets, especially has the greatest influence on the reducibility and the high-temperature strength, wherein the reducibility of the biomass carbon-containing pellets prepared from hematite is the best, the high-temperature strength is the highest, the reducibility and the low-temperature reduction chalking property of the biomass carbon-containing pellets prepared from vanadium titano-magnetite are the worst, and the strength after high-temperature reduction is the worst. In addition, the molding temperature and the molding pressure have obvious influence on the cold strength of the biomass carbon-containing pellets, and the higher the molding temperature is, the higher the molding pressure is, and the higher the cold strength of the biomass carbon-containing pellets is.
Examples 15 to 17
Examples 15 to 17 respectively provide a method for preparing biomass carbon-containing pellets for blast furnace ironmaking, which is different from example 4 in that biomass raw materials are used, and specific values corresponding to the examples are shown in table 7. Other preparation methods and the same as example 4 are not described here.
Table 7 types of biomass raw materials corresponding to examples 15 to 18
| Examples | Species of biomass |
| Example 15 | Rice straw |
| Example 16 | Soybean straw |
| Example 17 | Waste timber |
| Example 18 | Garden trimming object |
The performance of the biomass carbonaceous pellets prepared in examples 15 to 17 was tested and the results are shown in table 8.
Table 8 performance of examples 15-17 in preparing biomass carbon-containing pellets
| Examples | Example 15 | Example 16 | Example 17 | Example 18 |
| Intensity of cold state (N/P) | 1003 | 1060 | 1180 | 1055 |
| Reduction Strength at 900 ℃ (N/P) | 501 | 522 | 585 | 525 |
| Reduction Strength at 1000 ℃ (N/N) | 732 | 822 | 897 | 821 |
| Reduction Strength at 1100 ℃ (N/P) | 1359 | 1621 | 1766 | 1592 |
| Reduction strength (N/N) at 1200 DEG C | 2018 | 2362 | 2387 | 2252 |
| Reducibility (%) | 89 | 93 | 92 | 93 |
| Reduction expansion index (%) | 7.9 | 6.4 | 5.1 | 6.0 |
| Low temperature reduction degradation index (%) | 91 | 94 | 95 | 93 |
As can be seen from Table 8, the obtained biomass carbon-containing pellets prepared in examples 15 to 17 can meet the requirements of blast furnace injection smelting, wherein the obtained biomass carbon-containing pellets prepared by using waste timber as biomass raw materials have the best performance, the cold strength reaches 1180N/min, the 900 ℃ reduction strength 585N/min, the 1000 ℃ reduction strength 896N/min, the 1100 ℃ reduction strength 1766N/min and the 1200 ℃ reduction strength 2387N/min, the reducibility is 92%, the reduction expansion index is 5.1%, the low-temperature reduction degradation index is 95%, and the requirements of blast furnace smelting on the quality of the biomass carbon-containing pellets can be met.
In summary, the invention provides a biomass carbon-containing pellet for blast furnace ironmaking and a preparation method thereof, which are used for preparing biomass hydrothermal carbon with low alkali metal content and high hot-melt extraction rate by crushing biomass and then carrying out hydrothermal carbonization; performing pyrolysis carbonization treatment on one part of the biomass hydrothermal carbon to prepare low-volatile biomass carbon, and performing hot-melt extraction on the other part of the biomass hydrothermal carbon to prepare a biomass high-temperature binder; and crushing and uniformly mixing biomass charcoal, a biomass high-temperature binder, iron ore powder and a solvent, and performing hot press molding to obtain biomass carbon-containing pellets. Through the mode, the biomass with high volatile, high moisture and high harmful element content can be prepared into the biomass-based reducing agent with high fixed carbon content, high cohesiveness and low harmful element content and the binder, and the high-quality biomass carbon-containing pellets which can be used as blast furnace smelting furnace burden are prepared through a hot press forming method, so that the carbon emission in the iron-making production process is effectively reduced.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (12)
1. The preparation method of the biomass carbon-containing pellets for blast furnace ironmaking is characterized by comprising the following steps:
s1, removing impurities from biomass raw materials, crushing, and preparing biomass hydrothermal carbon with alkali metal content lower than 0.3% and hot-melt extraction rate higher than 15% by adopting a hydrothermal carbonization technology;
s2, carrying out pyrolysis carbonization treatment on part of the biomass hydrothermal carbon prepared in the step S1 to prepare biomass carbon with the volatile content lower than 15%; carrying out solvent hot-melting extraction on the other part of the biomass hydrothermal carbon to prepare a biomass high-temperature binder;
s3, respectively crushing the iron ore powder, the flux and the biomass charcoal and the biomass high-temperature binder prepared in the step S2, and uniformly mixing to obtain a mixture;
and S4, performing hot press molding on the mixture obtained in the step S3 to obtain biomass carbon-containing pellets.
2. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 1, which is characterized in that: in the step S1, the hydrothermal carbonization temperature of the hydrothermal carbonization technology is 200-260 ℃, the hydrothermal carbonization time is 60-180 min, and the solid-liquid ratio of the biomass raw material to the water is 1:3-1:5; the ash content of the prepared biomass hydrothermal carbon is lower than 7.5%, the volatile matter is lower than 65.8%, and the sulfur content is lower than 0.2%.
3. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 1, which is characterized in that: in the step S2, the pyrolysis and carbonization temperature is 500-900 ℃, and the pyrolysis and carbonization time is 60-240 min; the ash content of the prepared biomass charcoal is lower than 10.6%.
4. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 1, which is characterized in that: in the step S2, the temperature of the hot-melt extraction is 280-420 ℃, the solid-liquid ratio of the biomass hydrothermal carbon to the solvent in the hot-melt extraction process is 1:5-1:80, the time of the hot-melt extraction is 30-120 min, and the solvent is an organic solvent; the ash content of the prepared biomass high-temperature binder is less than 3.5%, the volatile content is less than 55.6%, and the caking index is more than 81.3%.
5. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 4, which is characterized in that: the solvent is N-methyl pyrrolidone.
6. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 1, which is characterized in that: in the step S3, after the crushing, the mass fractions of particles with the granularity smaller than 0.074mm in the biomass charcoal, the biomass high-temperature binder, the iron ore powder and the flux are respectively larger than 60%, 30%, 70% and 80%; the mass ratio of the biomass charcoal to the biomass high-temperature binder to the iron ore powder to the flux in the mixture is 20-30:5-10:70-75:3-5.
7. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 6, which is characterized in that: the mass ratio of the biomass charcoal to the biomass high-temperature binder to the iron ore powder to the flux in the mixture is 25:8:73:4.
8. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 1, which is characterized in that: in the step S4, the temperature of the hot press forming process is 350-550 ℃, the pressure is more than 15MPa, and the hot press time is more than 1min.
9. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 1, which is characterized in that: in the step S3, the iron ore powder is one or more of hematite, magnetite, limonite, vanadium titano-magnetite, sea sand ore and baiyuneboite, and the flux is one or more of quicklime, slaked lime, dolomite, serpentine and forsterite.
10. The method for preparing biomass carbon-containing pellets for blast furnace ironmaking according to claim 1, which is characterized in that: the biomass raw material is one or a mixture of more of agricultural waste, forestry waste and urban organic waste.
11. A biomass carbon-containing pellet for blast furnace ironmaking is characterized in that: the biomass carbon-containing pellets are prepared by the preparation method of any one of claims 1 to 10, and can replace sinter or pellet ore to be applied to blast furnace smelting.
12. The biomass carbon-containing pellet for blast furnace ironmaking according to claim 11, wherein: the cold state strength of the biomass carbon-containing pellets is more than 1000N/biomass carbon-containing pellets, the high-temperature reduction strength is more than 500N/biomass carbon-containing pellets, the reducibility is more than 75%, the reduction expansion index is less than 10%, and the low-temperature reduction degradation index is more than 92%.
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